CN102827553A - Pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive sheet Download PDF

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Publication number
CN102827553A
CN102827553A CN2012102027796A CN201210202779A CN102827553A CN 102827553 A CN102827553 A CN 102827553A CN 2012102027796 A CN2012102027796 A CN 2012102027796A CN 201210202779 A CN201210202779 A CN 201210202779A CN 102827553 A CN102827553 A CN 102827553A
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CN
China
Prior art keywords
layer
adhesive sheet
weight
bond layer
block
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Pending
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CN2012102027796A
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Chinese (zh)
Inventor
内田翔
木户章文
森本政和
林圭治
泽﨑良平
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN102827553A publication Critical patent/CN102827553A/en
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    • G02B1/105—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/005—Diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/045—Presence of homo or copolymers of ethene in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer
    • C09J2453/005—Presence of block copolymer in the release coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2471/00—Presence of polyether
    • C09J2471/005—Presence of polyether in the release coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2848—Three or more layers

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)

Abstract

Provided is a pressure-sensitive adhesive sheet having good unwinding property from a roll body or the like and excellent antistatic property, and suitable for a surface protective film or the like. The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet including a back surface layer (A), a backing layer (B), and a pressure-sensitive adhesive layer (C), the back surface layer (A) and the pressure-sensitive adhesive layer (C) being outermost layers. The back surface layer (A) contains a block polymer formed of a block of a polyolefin and a block of a hydrophilic polymer at a content of 7 to 50 wt%, and the back surface layer (A) contains a releasing agent at a content of 2 to 20 wt%.

Description

Adhesive sheet
Technical field
The present invention relates to a kind of adhesive sheet.More specifically, relate to following adhesive sheet, it contains back layer, substrate layer and bond layer, and this back layer and this bond layer are outermost layer, and this adhesive sheet is good from the warp property of coiling body etc., and has excellent static resistance, is applicable to surface protection film etc.
Background technology
Employed adhesive sheet mainly is made up of plastic material in the surface protection films etc.Therefore, electrical insulating property is high, when rubbing or peeling off, produces static.If use the surface protection film of such adhesive sheet, then when peeling off, produce static as opticses such as polaroids.If will the residual state optics down of the static that as above produces be assembled into liquid crystal panel and to liquid crystal applied voltages, then produce the orientation loss of liquid crystal molecule, the problem of generation defective on liquid crystal panel.In addition, if produce static, then also produce the problem that attracts dust or chip.
Therefore, studied adhesive sheet has been implemented various antistatic treatment.
Report has following method: in the caking agent of adhesive sheet, add low molecular tensio-active agent, tensio-active agent is needed on from caking agent is carried out antistatic (with reference to patent documentation 1) by bur.But in such method, the low molecular tensio-active agent of interpolation is prone to ooze out in adhesive surface, worries being polluted by bur.Therefore, under the situation of used for optical part surface protection film, can produce the problem of the optical characteristics of damage optics in the adhesive application that will be added with low molecular tensio-active agent especially.
Report has the method (with reference to patent documentation 2) of electroconductive stuffing as static inhibitor of using.But if use electroconductive stuffing, therefore the then damage transparency, produces the problem that is not preferably applied to as the adhesive sheet of used for optical part surface protection film.
Recently, as static inhibitor, the polymer static inhibitor of the block polymer of the block that proposes to have a kind of conduct to comprise polyolefinic block and hydrophilic polymer.
The adhesive sheet that the polymer static inhibitor is arranged as use; Report has a kind of adhesive sheet; It obtains as follows: come out to prepare to contain the multilayer body of the antistatic layer and the substrate layer of polymer static inhibitor through double-layer coextrusion, form bond layer (with reference to patent documentation 3) in the substrate layer side coating acrylic-based adhesives of this multilayer body.But, owing to must form bond layer through coating, so there is the high problem of manufacturing cost.In addition, exist from the problem of the warp property difference of coiling body etc.
The adhesive sheet that the polymer static inhibitor is arranged as use; Report has a kind of adhesive sheet, and it carries out three-layer co-extruded go out to obtain (with reference to patent documentation 4) with the substrate layer that contains the polymer static inhibitor, middle layer, styrene-ethylene-butylene-styrene segmented copolymer class bond layer.But, exist from the problem of the warp property difference of coiling body etc.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 9-165460 communique
Patent documentation 2: TOHKEMY 2007-9135 communique
Patent documentation 3: TOHKEMY 2008-174727 communique
Patent documentation 4: TOHKEMY 2010-59218 communique
Summary of the invention
Invent problem to be solved
The present invention accomplishes in order to solve above-mentioned existing problem, and its purpose is to provide a kind of adhesive sheet, and its warp property from coiling body etc. is good, and has excellent static resistance, is applicable to surface protection film etc.
Be used to solve the method for problem
Adhesive sheet of the present invention, it contains back layer (A), substrate layer (B) and bond layer (C), and this back layer (A) and this bond layer (C) they are outermost layer, wherein,
This back layer (A) is with containing of 7～50 weight % of the proportional block polymer that contains the block that comprises polyolefinic block and hydrophilic polymer,
This back layer (A) is with containing of 2～20 weight % of the proportional releasing agent that contains.
Preferred embodiment, above-mentioned bond layer (C) is being measured 23 ℃ of temperature, peeling rate 10m/ minute, when peel angle 180 is spent, is being 0.8～4N/20mm with respect to the initial stage bonding force of acrylic panel.
Preferred embodiment, above-mentioned bond layer (C) contains and is selected from least a in polyolefin resin and the styrene resin.
Preferred embodiment, adhesive sheet of the present invention is shaped the formation material compositions coextrusion of the formation material (c) of formation material (b) that contains the formation material (a) of above-mentioned back layer (A), above-mentioned substrate layer (B) and above-mentioned bond layer (C) and integrated obtaining.
Preferred embodiment, adhesive sheet of the present invention is a surface protection film.
Preferred embodiment, adhesive sheet of the present invention is the used for optical part surface protection film.
The effect of invention
According to the present invention, a kind of adhesive sheet can be provided, its warp property from coiling body etc. is good, has excellent static resistance, is applicable to surface protection film etc.
Description of drawings
Fig. 1 is the constructed profile of the adhesive sheet of preferred implementation of the present invention.
Embodiment
" " A. adhesive sheet " "
Adhesive sheet of the present invention contains back layer (A), substrate layer (B) and bond layer (C), and this back layer (A) and this bond layer (C) are outermost layer.Adhesive sheet of the present invention can be the trilaminar multilayer body that is only formed by back layer (A), substrate layer (B) and bond layer (C), also can be the multilayer body more than four layers that forms of one deck at least arbitrarily by back layer (A), substrate layer (B), bond layer (C) and other.
Back layer (A) can be merely one deck, also can be two-layer above multilayer body.Substrate layer (B) can be merely one deck, also can be two-layer above multilayer body.Bond layer (C) can be merely one deck, also can be two-layer above multilayer body.
Fig. 1 is the constructed profile of the adhesive sheet of preferred implementation of the present invention.In Fig. 1, adhesive sheet 100 possesses back layer (A) 10, substrate layer (B) 20 and bond layer (C) 30.
The thickness of adhesive sheet of the present invention can be set at suitable thickness arbitrarily according to purposes.The thickness of adhesive sheet of the present invention is preferably 5 μ m～200 μ m, and more preferably 10 μ m～100 μ m are more preferably 20 μ m～60 μ m.
Adhesive sheet of the present invention is preferably through coextrusion and is shaped and integrally formed sheet.That is, the adhesive sheet of the present invention formation material compositions of formation material (c) that preferably will contain formation material (b) and the above-mentioned bond layer (C) of the formation material (a) of above-mentioned back layer (A), above-mentioned substrate layer (B) carries out coextrusion and is shaped and integrated obtaining.
Adhesive sheet of the present invention can be used in suitable purposes arbitrarily.Adhesive sheet of the present invention is because good from the warp property of coiling body etc., and has excellent static resistance, so as preferred use, can enumerate surface protection film, as preferred purposes, is the used for optical part surface protection film.
The 10m/ of adhesive sheet of the present invention minute warp power is preferably below the 0.6N/20mm, more preferably below the 0.55N/20mm, is more preferably below the 0.5N/20mm, is preferably especially below the 0.45N/20mm, most preferably is below the 0.4N/20mm.As stated, adhesive sheet of the present invention is very excellent from the warp property of coiling body etc.Therefore, for example can be widely used in various uses as rolled body (roll body) etc.The detailed content of the measuring method of warp power is explained in the back.
The sheet resistance value of the back layer of adhesive sheet of the present invention (A) is preferably less than 1 * 10 14Ω/, more preferably 1 * 10 13Below Ω/, be more preferably 1 * 10 12Below Ω/, be preferably 1 * 10 especially 11Below Ω/.As stated, the static resistance of adhesive sheet of the present invention is very excellent.Therefore, when rubbing or peeling off, be difficult for producing static, can suppress to attract dust and chip effectively.The detailed content of the measuring method of sheet resistance value is explained in the back.
Adhesive sheet of the present invention is under the condition of measuring 23 ℃ of temperature, peeling rate 10m/ minute, peel angle 180 degree; Bond layer (C) is preferably 0.8～4N/20mm with respect to the initial stage bonding force of acrylic panel; 1～3.5N/20mm more preferably; Be more preferably 1.2～3N/20mm, be preferably 1.5～2.5N/20mm especially.As stated, in the adhesive sheet of the present invention, bond layer (C) has the size of appropriateness with respect to the initial stage bonding force of acrylic panel, therefore, fits fully, is easy to peel off and all is easy to carry out, and can be widely used in various uses.The detailed content of the measuring method of initial stage bonding force is explained in the back.
" A-1. back layer (A) "
Back layer (A) preferably contains can form sheet or membranaceous thermoplastic resin.Consider that from having thermotolerance and solvent resistance and having flexual aspect back layer (A) is preferably polyolefin resin.(A) has pliability through back layer, just can easily be wound into web-like, can carry out various processing easily.
As polyolefin resin, for example can enumerate: multipolymer of polythylene resin, propylene resin, ethene and polar monomer that constitute by propylene or that constitute by propylene composition and ethene composition etc.
As polyolefin resin; More specifically; For example can enumerate: new LDPE (film grade), straight chain shape new LDPE (film grade), Vestolen PP 7052; Poly-1-butylene, gather-4-methyl-1-pentene, ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene 4 methyl 1 pentene copolymer, ethene 1-octene copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.; Wherein, As back layer (A), preferred new LDPE (film grade), straight chain shape new LDPE (film grade), ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-4 methyl 1 pentene copolymer, ethene-1-octene copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc. contain the resin of ethene composition.
The resinous principle of back layer (A) can only be made up of a kind of resinous principle, also can be made up of two or more resinous principles.
Back layer (A) can be merely one deck, also can be two-layer above multilayer body.Layer (A) be under the situation of two-layer above multilayer body overleaf, the preferred mutual applying through the fusion coextrusion of these each layers.
Back layer (A) preferably contains the block polymer of block as comprising of polymer static inhibitor polyolefinic block and hydrophilic polymer.Through containing such block polymer, can give back layer (A) excellent static resistance.
The polyolefinic block of such block polymer is preferably brought into play and is used in the resin that forms back layer (A) dispersive function equably.In addition, the block of the hydrophilic polymer of such block polymer is preferably brought into play and is prevented the charged function of back layer (A).Through containing such block polymer, this block polymer disperses in the layer (A) overleaf equably, can show stable static resistance, and can form the high back layer (A) of the transparency.Through using such block polymer, even processing such as the cloth wipings of washing, wet, the static resistance of back layer (A) also can descend hardly, can show stable static resistance.In addition, through using such block polymer, improved the transparency of back layer (A), therefore adhesive sheet of the present invention can be used as the surface protection film of optics.
The polyolefinic block that constitutes block polymer is preferably the polymkeric substance or the multipolymer of terminal olefin.As terminal olefin, for example can enumerate: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 3-methyl butene-1,4-methylpentene-1,3-methyl hexene-1 etc.
The block of polyolefinic block and hydrophilic polymer is preferably by chemically bonded.As such key, for example can enumerate: ester bond, amido linkage, ehter bond, urethane bonds, imide bond etc.Block through polyolefinic block and hydrophilic polymer alternately carries out bonding repeatedly via such key, can form block polymer.The molecular end of polyolefinic block is preferably with carrying out modification with the functional group of the molecular end functional group reactions of the block of hydrophilic polymer.As such functional group, for example can enumerate: carboxylic acid group, hydroxyl, amino, anhydride group 、 oxazolinyl, epoxy group(ing) etc.Functional group as such is preferably the carboxylic acid group.
Polyolefinic block can be merely two terminal-modified polyolefinic blocks, can be merely single terminal-modified polyolefinic block, also can be their mixture.
The number-average molecular weight of polyolefinic block is preferably 800～50000, and more preferably 1000～30000, be more preferably 2000～20000, be preferably 2500～10000 especially.
As the hydrophilic polymer of the block of hydrophilic polymer, for example can enumerate: polyethers, the hydrophilic polymer that contains polyethers, cation property copolymer, anionic property polymkeric substance etc.
As polyethers, for example can enumerate: polyether glycol, polyether diamine, their modifier etc.
The number-average molecular weight of polyethers is preferably 150～20000, and more preferably 300～20000, be more preferably 1000～15000, be preferably 1200～8000 especially.
As the hydrophilic polymer that contains polyethers, for example can enumerate: have polyether glycol the segmental polyether ester amides, have polyether glycol segmental polyetheramides imide, have polyether glycol the segmental polyether ester, have polyether diamine the segmental polyetheramides, have the segmental poly(ether-urethene) of polyether glycol or polyether diamine etc.
The number-average molecular weight of the hydrophilic polymer of the polyethers that contains is preferably 800～50000, and more preferably 1000～30000.
As cation property copolymer, for example can enumerate: have preferred 2～80 of separating, the more preferably polymkeric substance of 3～60 cationic groups by the nonionic molecular chain at intramolecularly.
The number-average molecular weight of cation property copolymer is preferably 500～20000, and more preferably 1000～15000, be more preferably 1200～8000.
As the anionic property polymkeric substance, for example can enumerate: will have the dicarboxylicacid of alkylsulfonyl and have glycol or polyethers as essential structural unit, and in a part, have preferred 2～80, the more preferably anionic property polymkeric substance of 3～60 alkylsulfonyls.
The number-average molecular weight of anionic property polymkeric substance is preferably 500～20000, and more preferably 1000～15000, be more preferably 1200～8000.
The block polymer that can be contained in back layer (A) preferably can be made through utilizing any appropriate means that the block of polyolefinic block and hydrophilic polymer is carried out polymerization.For example can be through under reduced pressure, 200～250 ℃ of blocks with polyolefinic block and hydrophilic polymer carry out polyreaction and make.
Consider that from the viewpoint of back layer (A) being given effectively static resistance the number-average molecular weight that can be contained in the block polymer of back layer (A) is preferably 2000～60000, more preferably 5000～40000, be more preferably 8000～30000.
The block polymer that can be contained in back layer (A) for example can be made through the method for record in TOHKEMY 2001-278985 communique, the TOHKEMY 2003-48990 communique etc.
The block polymer that can be contained in back layer (A) for example can obtain as " PELESTAT " of Sanyo Chemical Industries, Ltd.'s system serial form.For example can enumerate 300,303,230 in " PELESTAT " series of Sanyo Chemical Industries, Ltd.'s system etc.
The block polymer of the block that comprises polyolefinic block and hydrophilic polymer in the back layer (A) to contain proportional be 7～50 weight %; Be preferably 7～40 weight %; Be more preferably 8～35 weight %, be preferably 9～30 weight % especially, most preferably be 10～25 weight %.Containing of the block polymer of the block that comprises polyolefinic block and hydrophilic polymer in the back layer (A) is proportional when being lower than 7 weight %, might give static resistance effectively to back layer (A).Containing of the block polymer of the block that comprises polyolefinic block and hydrophilic polymer in the back layer (A) is proportional as if surpassing 50 weight %, and then the outward appearance of back layer (A) might variation.
Consider from the viewpoint of further raising static resistance, can contain an alkali metal salt, alkaline earth salt in the layer (A) overleaf.
It is 0.01～10 weight % with respect to the block polymer of the block that comprises polyolefinic block and hydrophilic polymer preferably that an alkali metal salt and alkaline earth salt total contains proportional, more preferably 0.01～5 weight %.
Contain releasing agent in the layer (A) overleaf.
As releasing agent, for example can enumerate: fatty acid acyl amine releasing agent, silicone based releasing agent, fluorine class releasing agent, chain alkyl class releasing agent etc.From forming separability and the more viewpoint consideration of excellent peel ply of balance that prevents because of oozing out the contaminative that causes, be preferably fatty acid acyl amine releasing agent, more preferably chain alkyl class releasing agent.Releasing agent in the back layer (A) contain proportional 2～20 weight % that are preferably, more preferably 2～15 weight % are more preferably 2～10 weight %.
The thickness of back layer (A) is preferably 1～100 μ m, and more preferably 1～80 μ m is more preferably 2～70 μ m, is preferably 2～50 μ m especially, most preferably is 2～30 μ m.
Any suitable additive that also can be overleaf contains other in the layer (A).As such additive, for example can enumerate: weighting agent, pigment, UV light absorber, inhibitor, heat-resisting stabilizing agent, lubricant, antiblocking agent etc.
" A-2. substrate layer (B) "
Substrate layer (B) preferably contains can form sheet or membranaceous thermoplastic resin.Consider that from having thermotolerance and solvent resistance and having flexual aspect substrate layer (B) is preferably polyolefin resin.(B) has pliability through substrate layer, just can easily be wound into web-like, can carry out various processing easily.
As polyolefin resin, for example can enumerate: multipolymer of polythylene resin, propylene resin, ethene and polar monomer that constitute by propylene or that constitute by propylene composition and ethene composition etc.
As polyolefin resin; More specifically; For example can enumerate: new LDPE (film grade), straight chain shape new LDPE (film grade), Vestolen PP 7052, poly-1-butylene, gather-4-methyl-1-pentene, ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-4 methyl 1 pentene copolymer, ethene-1-octene copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.
Substrate layer (B) can be merely one deck, also can be two-layer above multilayer body.At substrate layer (B) is under the situation of the multilayer body more than two-layer, the preferred applying mutually through the fusion coextrusion of these each layers.
Can in substrate layer (B), add any suitable additive.As such additive, for example can enumerate weighting agent, pigment, UV light absorber, inhibitor, heat-resisting stabilizing agent, lubricant, antiblocking agent etc.
The thickness of substrate layer (B) is preferably 5～300 μ m, and more preferably 10～250 μ m are more preferably 15～200 μ m, are preferably 20～150 μ m especially.Thickness at substrate layer (B) is lower than under the situation of 5 μ m, and substrate layer when peeling off (B) might damaged or fracture.Surpass under the situation of 300 μ m at the thickness of substrate layer (B), the deflection of substrate layer (B) might become excessive and after stickup, produce easily and float etc.
" A-3. bond layer (C) "
Bond layer (C) is as long as the layer that the material of the formation caking agent of serving as reasons constitutes just can adopt suitable layer arbitrarily.In order fully to show effect of the present invention, such bond layer (C) preferably contains at least a in polyolefin resin and the styrene resin.At least a in polyolefin resin and the styrene resin of being selected from the bond layer (C) contains proportional being preferably more than the 50 weight %; More preferably more than the 60 weight %; Be more preferably more than the 70 weight %, be preferably especially more than the 80 weight %, most preferably be more than the 90 weight %.
As such polyolefin resin, can adopt suitable polyolefin resin arbitrarily.As such polyolefin resin, for example can enumerate noncrystalline polyolefin class elastomerics.
As noncrystalline polyolefin class elastomerics, for example can enumerate: ethylene-propylene rubber(EPR), the elastomerics that constitutes by ethene and terminal olefin, the polypropylene-based resin that shows cementability etc.Can preferably enumerate polypropylene-based resins such as Atactic Polypropelene class.Polypropylene-based resin just can adopt suitable polypropylene-based resin arbitrarily as long as have caoutchouc elasticity in the use temperature zone.
Wherein, noncrystalline polyolefin class elastomerics has the amorphism of crystalline structure.As having non-crystalline confirmation method, for example can be set forth in the dissolubility test in the normal heptane.Particularly; Noncrystalline polyolefin class elastomerics is dissolved in the normal heptane with the concentration of 10 weight %, measures its solubleness, at this moment; Consoluet in fact situation being made as under 100% the situation, is that elastomerics more than 90% is made as and has amorphism with solubleness.
As polypropylene-based resin, for example can enumerate: propylene-alpha-olefin copolymers, propylene-ethylene-alpha-olefin copolymer etc.
As terminal olefin, for example can enumerate: 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene etc.Wherein, preferred 1-butylene, 1-hexene, 1-octene, 4-methyl isophthalic acid amylene.It is a kind of that terminal olefin can be merely, also can be for two or more.
As polypropylene-based resin, can preferably enumerate amorphousness propylene-(1-butylene) multipolymer.Amorphousness propylene-(1-butylene) multipolymer preferably uses metallocene catalyst to obtain through propylene and 1-butylene are carried out copolymerization.Amorphousness propylene-(1-butylene) multipolymer that has the copolymerization of metallocene catalyst to obtain through use shows narrow MWD (for example, below 2).If use amorphousness propylene-(1-butylene) multipolymer that shows so narrow MWD, then can prevent oozing out of low molecular weight compositions.
The structural unit that is derived from propylene in amorphousness propylene-(1-butylene) multipolymer contain proportional 80～99 moles of % that are preferably, more preferably 85～99 moles of % are more preferably 90～99 moles of %.If not containing of the structural unit that is derived from propylene in crystalloid propylene-(1-butylene) multipolymer is proportional for such scope, then can access the bond layer (C) of the balance excellence of toughness and flexibility, can show effect of the present invention more effectively.
The structural unit that is derived from 1-butylene in amorphousness propylene-(1-butylene) multipolymer contain proportional 1～15 mole of % that is preferably, more preferably 1～10 mole of %.If not the structural unit that is derived from 1-butylene in crystalloid propylene-(1-butylene) multipolymer contains proportional such scope that is, then can obtain the excellent bond layer (C) of balance of toughness and flexibility, and can show effect of the present invention more effectively.
As the copolymerization structure of amorphousness propylene-(1-butylene) multipolymer, can adopt suitable copolymerization structure arbitrarily.As such copolymerization structure, for example can enumerate segmented copolymer, random copolymers etc.
The weight-average molecular weight (Mw) of amorphousness propylene-(1-butylene) multipolymer is preferably more than 200000, and more preferably 200000～500000, be more preferably 200000～300000.As long as the weight-average molecular weight (Mw) of amorphousness propylene-(1-butylene) multipolymer just can access the bond layer (C) with suitable bonding force in such scope, can show effect of the present invention more effectively.
Contain at bond layer (C) under the situation of amorphousness propylene-(1-butylene) multipolymer, in order to regulate the bonding force of bond layer (C), bond layer (C) also can further contain the crystalline polypropylene resinoid.(C) contains the crystalline polypropylene resinoid through bond layer, can appropriateness reduce the bonding force of bond layer (C) and increase storage elastic modulus.Further contain under the resinoid situation of crystalline polypropylene at bond layer (C), the crystalline polypropylene in the bond layer (C) is resinoid contain proportional can according to the bonding force of expectation and storage elastic modulus be set at any suitable contain proportional.As such crystalline polypropylene resinoid contain proportional; Preferably be preferably 0～50 weight % with respect to amorphousness propylene-(1-butylene) multipolymer and the resinoid gross weight of crystalline polypropylene; More preferably 0～40 weight % is more preferably 0～30 weight %.
As styrene resin, can preferably enumerate styrene analog thermoplastic elastomer.As styrene analog thermoplastic elastomer, as long as can carry out film and be shaped and just can adopt any suitable styrene analog thermoplastic elastomer through melt extruding.Styrene analog thermoplastic elastomer is meant that use contains the monomer component of at least a styrene monomer at least and the elastomerics that obtains.It is a kind of that the styrenic thermoplastic elastomer can be merely, also can be for two or more.
As styrene analog thermoplastic elastomer; For example can enumerate: styrene-ethylene-butylene copolymer styrenic AB type Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks such as (SEB); The hydrogenation thing of the hydrogenation thing of styrene-butadiene-styrene multipolymer (SBS), SBS (styrene-ethylene-butylene-styrene multipolymer (SEBS)), styrene-isoprene-styrene copolymer-(SIS), SIS (styrene-ethylene-propylene-styrene multipolymer (SEPS)), vinylbenzene-isobutylene-styrene copolymer styrenic ABA type triblock copolymers such as (SIBS); Styrene-butadiene-styrene-divinyl styrenic ABAB type Tetrablock copolymers such as (SBSB); Styrene-butadiene-styrene-butadiene-styrene styrenic ABABA type five segmented copolymers such as (SBSBS) have the styrenic block copolymers such as styrenic segmented copolymer of these above AB repeating units.In addition, the ethene property pair keys that also can enumerate SBR styrene butadiene rubbers styrenic random copolymerss such as (SBR) carry out the hydrogenation thing that hydrogenation obtains.
Styrene block structure in the styrenic block copolymer contain proportional 5～40 weight % that are preferably, more preferably 7～30 weight % are more preferably 9～20 weight %.Under containing of the styrene block structure proportional situation that is less than 5 weight %, owing to the not enough cull that is easy to generate of bounding force of bond layer (C).Under containing of styrene block structure proportional situation more than 40 weight %, bond layer (C) hardening might can't obtain the cementability good with respect to uneven surface.
Have at styrenic block copolymer under the situation of ethene-butylene blocks structure; The structural unit that is derived from butylene in ethene-butylene blocks structure contain proportional being preferably more than the 50 weight %; More preferably more than the 60 weight %; Be more preferably more than the 70 weight %, be preferably 70～90 weight % especially.As long as be derived from butylene structural unit contain proportional in such scope, wettability and excellent in adhesion then, though can access also can be bonding well with respect to uneven surface bond layer (C).
Bond layer (C) can contain other suitable composition arbitrarily as required.As other composition, for example can enumerate: tackifier, tenderizer, inhibitor; Olefine kind resin, silicone based resin, propylene liquid acid copolymer, polymine; Fatty acid amide, SULPHOSUCCINIC ACID ESTER, hindered amine light stabilizer, UV light absorber; Heat-resisting stabilizing agent, weighting agent or pigment such as quicklime, Natural manganese dioxide, silicon-dioxide, zinc oxide, titanium oxide, other additive etc.The kind of other composition that can contain in the bond layer (C), number and amount can suitably be set according to purpose.The amount of other composition is preferably below the 5 weight % with respect to bond layer (C) integral body, more preferably below the 1 weight %.
Tackifier are effective to improving bonding force.Contain under the situation of tackifier at bond layer (C), consider to prevent to produce cull because of the reduction of bounding force, the tackifier in the bond layer (C) contain proportional be set at suitable arbitrarily contain proportional.The proportional resinous principle with respect to bond layer (C) that contains of the tackifier in the bond layer (C) is preferably 1～60 weight %, and more preferably 3～50 weight % are more preferably 4～45 weight %, are preferably 5～40 weight % especially.
As tackifier, for example can enumerate: hydrocarbon tackifier, terpenes tackifier, rosin based tackifier, phenols tackifier, epoxies tackifier, polyamide-based tackifier, elastic system tackifier, ketone tackifier etc.Tackifier in the bond layer (C) can be merely a kind of, also can be for two or more.
As hydrocarbon tackifier; For example can enumerate: aliphatic category hydrocarbon resin, fragrant same clan hydrocarbon resin are (for example; Xylene resin etc.); Aliphatic category cyclic hydrocarbon resin, aliphatics fragrance same clan petroleum resin (for example, vinylbenzene-olefinic copolymer etc.), aliphatics alicyclic ring same clan petroleum resin, hydrogenated hydrocarbons resin, coumarone resinoid, coumarone-indenes resinoid etc.
As the terpenes tackifier; For example can enumerate: terpenoid resins such as α-Pai Xi polymkeric substance, beta-pinene polymer; Terpenoid resin (is for example carried out modification; Phenol modification, aromatic series modification, hydrogenation modification etc.) the modification terpenoid resin (for example, terpenes-phenolic resin, phenylethene modified terpenoid resin, hydrogenation terpenoid resin etc.) that obtains etc.
As the rosin based tackifier; For example can enumerate: unmodified rosin (pine gum) such as rosin (gum rosin), wood rosin; Through hydrogenation, disproportionation, polymerization etc. unmodified rosin (is for example carried out modified rosin that modification obtains; Staybelite, nilox resin, polymerized rosin, other through rosin of chemically modified etc.), other various rosin derivatives etc.
As the phenols tackifier, for example can enumerate: the alkylphenol of soluble phenolic resin (resol) type or phenolic varnish (novolac) type etc.
Tackifier also can be conduct and olefin resin or the tackifier commercially available with the blend of thermoplastic elastomer.
Tenderizer is effective to improving bonding force.Contain the situation of tenderizer at bond layer (C), the tenderizer in the bond layer (C) contain the proportional suitable amount arbitrarily that adopts.If containing of the tenderizer in the bond layer (C) is proportional excessive; Then has the trend that the cull when high temperature or outdoor exposure increases; Therefore; Tenderizer in the bond layer (C) contain proportional being preferably below the 40 weight %, more preferably below the 20 weight %, be more preferably below the 10 weight %.
As tenderizer, for example can enumerate: low-molecular-weight diolefinic polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer and their verivate etc.As this verivate, for example can enumerate: have OH or the basic verivate of COOH at an end or two ends.Particularly, can enumerate hydrogenated butadiene polymer glycol, hydrogenated butadiene polymer list alcohol, hydrogenated polyisoprene glycol, hydrogenated polyisoprene list alcohol etc.In order further to suppress the raising of bonding force, the hydrogenate of diolefinic polymers such as preferred hydrogenated butadiene polymer or hydrogenated polyisoprene or olefines tenderizer etc.Particularly, can enumerate " the Kuraprene LIR-200 " etc. of KURARAY Co., Ltd. system.Tenderizer in the bond layer (C) can be merely a kind of, also can be for two or more.
The molecular weight of tenderizer can be set at the amount of any appropriate.If the molecular weight of tenderizer is too small; Then might become from the reason of oozing out the pollution that causes of bond layer (C), on the other hand, if the molecular weight of tenderizer is excessive; The trend that the raising effect that lacks bonding force is then arranged; Therefore, the number-average molecular weight of tenderizer is preferably 5000～100000, and more preferably 10000～50000.
The thickness of bond layer (C) is preferably 1～50 μ m, and more preferably 2～40 μ m are more preferably 3～20 μ m.
Also can be as required be the surface treatment of purpose to the surperficial embodiment of bond layer (C) such as Corona discharge Treatment, uviolizing processing, flame treating, plasma treatment, sputter etching processing etc. with control cementability and sticking operation property etc.
Also can be as required supply before practical during, (C) temporarily pastes dividing plate protection to bond layer.
" " method of manufacture of B. adhesive sheet " "
Adhesive sheet of the present invention can be carried out the formation material compositions of the formation material (c) of the formation material (b) of the formation material (a) that contains back layer (A), substrate layer (B) and bond layer (C) that coextrusion is shaped and be integrated and obtain.
The formation material (a) of back layer (A) preferably contains polyolefin resin, comprises block polymer, the releasing agent of the block of polyolefinic block and hydrophilic polymer.As far as the formation material (a) of back layer (A), can preferably enumerate: 1) these materials are done and mixed and method of mixing with mixing machines such as tumbler mixer, ribbon blender, Henschel mixers; 2) these materials do are mixed after, carry out melting mixing and the method for pelletization through forcing machine; 3) make the masterbatch of these materials in advance, with above-mentioned mixing machine this masterbatch and polyolefin resin etc. are done and mixed and method of mixing etc.
The method that coextrusion is shaped can use forcing machine and coextrusion to carry out with mould and according to blow moulding, T modulus method etc. respectively to the formation material of each layer.Be shaped through this coextrusion, it is integrated and become multilayer body to be derived from each layer that respectively forms material.
When making adhesive sheet of the present invention, also can be to being shaped through above-mentioned coextrusion and the integrated multilayer body irradiation ionizing radiation that obtains.Particularly, for example can be before being wound into web-like or under the state that after being wound into web-like, winds off once more, to the multilayer body irradiation ionizing radiation that obtains.The irradiation of ionizing radiation is preferably carried out under the atmosphere of inactive gass such as nitrogen.As ionizing radiation, for example can enumerate: X ray, gamma-rays, ultraviolet ray, visible rays, electron beam etc.Consider from the high aspect of the production rate of the reactive behavior kind (active species) in when irradiation and to aspects such as soaking into of irradiation object thing are dark, as ionizing radiation, the preferred electron bundle.As electron beam source, for example can use various electron-beam accelerators such as Cockcroft, John Douglas Te-Wa Erdun type (Cockroft Walton type), model De Graff type (Van de Graafftype), resonance transformer type, insulating core transformer type, linear pattern, dynamitron type (Dynamitron type), high-frequency type.The irradiation of ionizing radiation can also can be shone from both sides from the side irradiation of multilayer body.Aspect simplified working procedures, the irradiation of ionizing radiation preferably imported multilayer body the ionizing radiation beam irradiating apparatus and shone ionizing radiation before being wound into web-like.Consider that from the viewpoint that improves interlayer tack and the rerum natura of keeping adhesive sheet the illuminated line amount of ionizing radiation is preferably 10～500kGy, more preferably 10～400kGy is more preferably 10～300kGy.For the acceleration voltage of ionizing radiation, can suitably select according to the kind of employed resin in the adhesive sheet and the thickness of adhesive sheet.The acceleration voltage of ionizing radiation is preferably the scope of 50～300kV usually.Ionizing radiation can be once irradiating, also can be for repeatedly (being preferably twice) irradiation.
Embodiment
Below, through embodiment the present invention is carried out brightly specifically, but the present invention does not receive any qualification of these embodiment.In addition, test and the evaluation method among embodiment etc. is described below.In addition, part is meant weight part.In addition, % is meant weight %.
< mensuration of weight-average molecular weight >
Under following condition, carrying out GPC measures.
Determinator: TOSOH Co., Ltd's system, model " HLC-8120GPC "
Chromatographic column: TOSOH Co., Ltd's system is connected in series TSKgel Super HZM-H/HZ4000+HZ3000+HZ2000 and use.
Column size: be respectively internal diameter 6.0mm * length 15.0cm
Column temperature: 40 ℃
Flow velocity: 0.6mL/ minute
Elutriant: THF
Sample IR: 20 μ L
Detector: RI (differential refractometer)
Standard test specimen: PS
< mensuration of sheet resistance value >
Under the atmosphere of 23 ℃ of temperature, humidity 50%RH, use resistrivity meter (Analytech of Mitsubishi Chemical system, Hiresta UP MCP-HT450 type) and measure according to JIS-K-6911.
< mensuration of warp power >
" high speed warp power " with JIS-Z-0237 (2009) is benchmark, as test sample, uses warp power determinator to measure warp power the adhesive sheet that is wound into web-like.In addition, for following condition, the condition that changes to JIS-Z-0237 (2009) record is measured, with the measured value of gained as warp power.
Measure temperature: 23 ℃
Measure humidity: 50%RH
The width of test film: 20mm
Draw speed: 10m/ minute
< mensuration of initial stage bonding force >
The adhesive sheet that is wound into web-like is wound off 5 layers, behind the adhesive tape outside cutting away, this adhesive sheet is expanded into length 300mm, width 20mm, as test sample.
As by bur, use acrylic panel (RAYON of Mitsubishi corporate system, Acrylite L), be pasted on by bur with line pressure 78.5N/cm, speed 0.3m/ minute, with it 23 ℃, the atmosphere held of humidity 50%RH 30 minutes.Then, under identical atmosphere, use universal tensile testing machine (Shimadzu Seisakusho Ltd.'s system, Autograph AG-IS) under the condition of peeling rate 10m/ minute, peel angle 180 degree with adhesive sheet from being peeled off by bur, measure the peeling force of this moment.Three samples are measured, with its MV as the initial stage bonding force.
[making example 1]: the manufacturing of stripper
With 100 parts by weight of ethylene-vinyl alcohol copolymer (KURARAY Co., Ltd. system; Trade(brand)name " Eval E-171B "; 44 moles of %) and 310 weight part octadecylisocyanate (Baotugu Chemical Industrial Co., Ltd's systems ethene structural unit:; Trade(brand)name " MILLIONATE O ") being dispersed in 2000 parts by weight of toluene, refluxed two hours in the limit, and the limit is separated from reflux in backflow and removed moisture.Then; Be cooled to 40 ℃; Add 300 weight part DMSO 99.8MIN.s; Is that 0.7 mode drips octadecylisocyanate (Baotugu Chemical Industrial Co., Ltd's system, trade(brand)name " MILLIONATE O ") while stirring with NCO with respect to the equivalence ratio of the hydroxyl of ethylene-vinyl alcohol copolymer, makes its reaction 4 hours at 120 ℃.Between this reaction period, the remaining NCO in the system is carried out quantitatively (2260cm with infrared spectrophotometer -1Near), the moment that disappears with this remaining group is as terminal point.
After reaction finishes, in reaction solution, add the water of 340 weight parts, reaction solution is carried out separatory.To use hermetic type pressure filter (Japan makes made, the sterilising filtration machine) to carry out pressure filtration this reaction solution as the reaction solution azeotropic dehydration of toluene layer after 1 hour at 110 ℃ at 30 ℃.The filtrating that obtains is injected in the methyl alcohol of 5000 weight parts, white depositions is separated out.After filtering out this throw out, clean with methyl alcohol, spinning, drying and crushing obtains the target stripper of 363 weight parts.
Contained content of impurities is 0.4 weight % in the stripper that obtains, and weight-average molecular weight is 1.13 * 10 5In addition, the method for calculation for the weight-average molecular weight of the total content (weight %) of the impurity that comprises in the stripper and stripper are described below.
The total content of contained impurity uses the GPC method to measure in the stripper.Device uses TOSOH Co., Ltd's system " TSKgel " (solvent: THF; Temperature: 40 ℃, flow: 0.6ml/ branch, concentration: 1.0mg/ml; Chromatographic column: super HZM-H/HZ4000/HZ3000/HZ2000; Detector: RI (installing built-in)), in the graph of molecular weight distribution that obtains, the polystyrene conversion molecular weight is in 3.0 * 10 3The value that the peak area of the composition below near the peak valley (mnm.) is represented with percentage with respect to the ratio of total peak area is made as the total content of impurity.
In addition, with above-mentioned stripper in the graph of molecular weight distribution that obtains equally of the total content of contained impurity, the weight-average molecular weight of stripper is for to be in 3.0 * 10 than polystyrene conversion molecular weight 3The weight-average molecular weight of the molecular weight constituent that near peak valley (mnm.) is high.
[embodiment 1]
With stripper, vinyl-vinyl acetate copolymer resinoid (Japanese Vilaterm system, NOVATEC LV440, d=0.936; MFR=2.0), polythylene resin (Japanese Vilaterm system, NOVATEC LC720, d=0.922; MFR=9.4), (Sanyo changes into system to PELESTAT 230; MFR=12) press the cooperation ratio shown in the table 1 through after twin screw extruder (L/D=51.5,180～200 ℃ of extruder temperatures, screw rod revolution 100rpm) extrudes; In water-bath, carry out pelletization after the cooling, with the formation material of the pellet that obtains as back layer.
With the formation material of Vilaterm (eastern Cao's system, Petrocene 186R) as substrate layer.
With the formation material of polyolefins adhering resin (Sumitomo Chemical Co's system, Tafthren H5002) as bond layer.
The above-mentioned material that respectively forms is carried out coextrusion through 3 kinds of 3 layers of blow mouldings (blow-up ratio 2.0, pulling speed 10m/ minute) for 180 ℃ in die temperature, obtain having back layer/substrate layer/adhesive sheet (1) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.The result is shown in table 2.
[embodiment 2]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (2) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[embodiment 3]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (3) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[embodiment 4]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (4) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[embodiment 5]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (5) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[embodiment 6]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (6) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[comparative example 1]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (C1) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[comparative example 2]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (C2) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[comparative example 3]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (C3) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[comparative example 4]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (C4) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[comparative example 5]
The cooperation ratio that kind as shown in table 1 of stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin and PELESTAT 230 is changed; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (C5) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[comparative example 6]
With stripper, vinyl-vinyl acetate copolymer resinoid, polythylene resin, PELESTAT 230 and surfactant type static inhibitor (Kao Corp's system; ELESTMASTER LL-10) cooperation ratio that kind as shown in table 1 changes; In addition; Likewise carry out with embodiment 1, obtain having back layer/substrate layer/adhesive sheet (C6) of the rhythmo structure of bond layer.
The thickness of back layer is 3 μ m, and the thickness of substrate layer is 30 μ m, and the thickness of bond layer is 5 μ m.
The result is shown in table 2.
[table 1]
Figure BDA00001773589700201
[table 2]
Utilizability in the industry
The adhesive sheet that obtains among the present invention can be used as surface protection film.In addition, needing can be preferred for visual used for optical part surface protection film.
Nomenclature
100 adhesive sheets
10 back layer (A)
20 substrate layers (B)
30 bond layers (C)

Claims (6)

1. adhesive sheet, it contains back layer (A), substrate layer (B) and bond layer (C), and this back layer (A) and this bond layer (C) they are outermost layer, it is characterized in that:
This back layer (A) is with containing of 7～50 weight % of the proportional block polymer that contains the block that comprises polyolefinic block and hydrophilic polymer,
This back layer (A) is with containing of 2～20 weight % of the proportional releasing agent that contains.
2. adhesive sheet as claimed in claim 1 is characterized in that:
Said bond layer (C) is being measured 23 ℃ of temperature, peeling rate 10m/ minute, when peel angle 180 is spent, is being 0.8～4N/20mm with respect to the initial stage bonding force of acrylic panel.
3. according to claim 1 or claim 2 adhesive sheet is characterized in that:
Said bond layer (C) contains and is selected from least a in polyolefin resin and the styrene resin.
4. like each described adhesive sheet in the claim 1～3, it is characterized in that:
Its formation material compositions coextrusion for the formation material (c) of the formation material (b) that will contain the formation material (a) of said back layer (A), said substrate layer (B) and said bond layer (C) is shaped and integrated obtaining.
5. like each described adhesive sheet in the claim 1～4, it is characterized in that:
It is a surface protection film.
6. adhesive sheet as claimed in claim 5 is characterized in that:
It is the used for optical part surface protection film.
CN2012102027796A 2011-06-17 2012-06-15 Pressure-sensitive adhesive sheet Pending CN102827553A (en)

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KR20120139575A (en) 2012-12-27
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